KR102079623B1 - Composition for matt coating decoration sheet and matt coating decoration sheet - Google Patents

Abstract

Provided is a composition for a matte decor sheet comprising a hydroxy group-containing (meth) acrylate resin, an isocyanate compound and a catalyst, wherein an equivalent ratio of hydroxy group (-OH) to isocyanate group (-NCO) is from 1: 0.1 to 1: 1. . In addition, it provides a matte decorative sheet including a hard coating layer and a matte release layer formed using the composition for the matte decorative sheet.

Description

COMPOSITION FOR MATT COATING DECORATION SHEET AND MATT COATING DECORATION SHEET}

It relates to a composition for matte decor sheet and to a matte decor sheet prepared using the same.

Articles, such as furniture, such as interior and exterior materials of a building, a desk, and a chair, are surface-treated in order to protect the surface and to give aesthetics. The surface treatment of an article is made variously according to a use, and in some cases, a high gloss surface treatment may be performed, and a matte surface treatment may be performed.

Such a surface treatment may be a method of coating, or a transfer method of applying irregularities to a surface by using an embossing roll or a transfer film having a large surface roughness.

The direct coating method using the matting agent to control the gloss has an increase in the amount of usage due to the decrease in the gloss, and the adsorption of contaminants is easy due to the material characteristics of the matting agent, and the use of the matting agent has a problem of deteriorating the appearance quality. In addition, the transfer method has a limitation in implementing a matte design having a glossiness of 5 or less, and thus, there is a disadvantage in that a product range is not various other than a semi-gloss product having a glossiness of 10-20.

Therefore, there is a need for a study that can simultaneously implement an excellent matt effect and pollution resistance.

One embodiment of the present invention provides a composition for a matte decor sheet that can be easily implemented to implement the appropriate roughness can be implemented at the same time excellent matting effect and excellent stain resistance.

Another embodiment of the present invention provides a matte decor sheet that implements excellent matting effect and stain resistance through a plurality of layers using the composition for the matte decor sheet.

In one embodiment of the present invention, a hydroxyl group-containing (meth) acrylate resin, an isocyanate compound and a catalyst, wherein the equivalent ratio of hydroxy group (-OH) to isocyanate group (-NCO) is 1: 0.1 to 1: 1 It provides a composition for matte decor sheet.

In another embodiment of the present invention, sequentially comprising a primer layer, a hard coating layer, a matte release layer and a base layer, wherein the hard coating layer and the matte release layer each comprises a thermoset of the composition for matte decor sheet, the matt The composition for decor sheet comprises the hydroxy group-containing (meth) acrylate-based resin, isocyanate-based compound and catalyst, the matte deco of the equivalent ratio of hydroxy group (-OH) to isocyanate group (-NCO) 1: 0.1 to 1: 1 Provide a sheet.

The matte decor sheet prepared using the matte decor sheet composition can be implemented at the same time excellent matting effect and stain resistance.

Specifically, by controlling the equivalent ratio of the hydroxyl group (-OH) to the isocyanate group (-NCO) of the composition for the matte decor sheet, the hard coating layer and the matte release layer prepared by using the same can realize the appropriate hardness and roughness, As a result, the effect of adjusting glossiness and improving stain resistance and scratch resistance can be obtained.

Figure 1 schematically shows a cross-section of the matte decorative sheet according to an embodiment of the present invention.
Figure 2 schematically shows a process of manufacturing a molded article using a matte decorative sheet according to an embodiment of the present invention.
FIG. 3 schematically illustrates an enlarged view of a cross section when the matte release layer includes a matting agent according to an embodiment of the present invention.

Advantages and features of the present invention, and a method for achieving them will be apparent with reference to the following embodiments. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various forms. The present embodiments are merely provided to complete the disclosure of the present invention, and to fully inform those skilled in the art the scope of the present invention, which is defined by the scope of the claims. It will be. Like reference numerals refer to like elements throughout.

In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. In the drawings, for convenience of description, the thicknesses of some layers and regions are exaggerated.

One embodiment of the present invention comprises a hydroxyl group-containing (meth) acrylate resin, an isocyanate compound and a catalyst, wherein the equivalent ratio of the hydroxy group (-OH) to the isocyanate group (-NCO) is from about 1: 0.1 to about It provides a composition for matte decor sheet of 1: 1.

The matte decorative sheet composition is a hard coating layer and a matte release layer formed therefrom by adjusting the equivalent ratio of the hydroxy group (-OH) to the isocyanate group (-NCO) contained in the range of about 1: 0.1 to about 1: 1 This excellent durability and stain resistance can be realized, and high surface hardness can be achieved.

The equivalent ratio refers to the ratio of the number of isocyanate group (-NCO) functional groups to the number of hydroxy group (-OH) functional groups. The hydroxyl group (-OH) and the isocyanate group (-NCO) may form a crosslinked structure by performing a urethane bonding reaction (-NH-CO-O-) with each other during thermal curing of the composition for the matte decor sheet. When the equivalent ratio of the hydroxy group (-OH) to the isocyanate group (-NCO) is less than about 1: 0.1, that is, when the number of the isocyanate group (-NCO) groups is too small compared to the number of hydroxy groups (-OH), Hardening of the composition for the matte decorative sheet is not good, may cause a problem that the scratch resistance of the matte decorative sheet is lowered. Further, when the equivalent ratio of the hydroxy group (-OH) to the isocyanate group (-NCO) is greater than about 1: 1, that is, when the number of the isocyanate group (-NCO) is too large compared to the number of the hydroxy group (-OH), After curing of the composition for matte decor sheet, the isocyanate group remains, which may cause a problem of causing a side reaction.

The composition for the matte decor sheet is the equivalent ratio of the isocyanate group (-NCO) and the hydroxy group (-OH) satisfying the above-mentioned range can secure a surface hardness excellent in the cured product thereof, and a hard coating layer formed using the same The matte release layer can impart excellent stain resistance and matte effect to the matte decor sheet.

The thermosetting material of the composition for the matte decor sheet may have a surface hardness of about HB to about 2H, for example. The 'surface hardness' is a result of measuring the surface of the thermoset using a pencil hardness tester (LT-PC2, electric pencil hardness tester), the surface hardness of the thermoset is satisfied by the thermosetting It may exhibit durability that does not easily wear to external friction. The surface hardness of the thermoset may be adjusted by appropriately controlling the composition of the composition for the matte decor sheet and the process conditions for curing it.

In one embodiment, the hydroxy group-containing (meth) acrylate-based resin may be a copolymer of a monomer component comprising an alkyl group-containing (meth) acrylate monomer and a hydroxy group-containing (meth) acrylate monomer.

Examples of the alkyl group-containing (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth). ) Acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n -Octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) acrylate, glycidyl methacrylate) (GMA) And it may include one or more selected from the group consisting of, but is not limited thereto.

The hydroxy group-containing (meth) acrylate monomers are, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate or 2-hydroxypropylene glycol (meth) acrylate, and their It may include at least one selected from the group containing a combination, but is not limited thereto.

The hydroxy group-containing (meth) acrylate-based resin may have a weight-average molecular weight (Mw) of about 40,000 to about 60,000. By maintaining the weight average molecular weight in the above range, it is possible to realize the effect of improving the degree of curing to the maximum. If the weight average molecular weight is less than the range may cause a problem that the flexibility is lowered, if the weight average molecular weight is greater than the range may cause a problem that the curing reaction of the isocyanate group and the hydroxyl group is delayed.

The hydroxyl group-containing (meth) acrylate resin may have a glass transition temperature (Tg) of about 40 ° C to about 120 ° C. Since the hydroxy group-containing (meth) acrylate-based resin has a glass transition temperature (Tg) in the above range, thermosetting of the composition for matte decor sheet can be made at a relatively low temperature. When the glass transition temperature is less than the above range, the hard coating layer formed of the matte decorative sheet composition may not secure sufficient surface hardness. If the glass transition temperature is above the above range, the curing rate may be too high in the manufacturing process, thereby degrading workability. .

The hydroxy group-containing (meth) acrylate-based resin may have a hydroxyl value (OH value) of about 20 to about 100. The 'hydroxy value' represents the number of g of a hydroxyl group (OH group) contained per 1,000 g of the resin. By the resin exhibiting a hydroxy value (OH value) in the above range, the hard coating layer formed by using the composition for the matte decorative sheet can ensure an appropriate degree of curing, it is possible to obtain an excellent surface strength. If the hydroxy value of the resin exceeds the above range may be good in terms of reactivity, there is a fear that the layer or sheet formed of the composition for the matte decorative sheet may not secure the appropriate degree of curing.

The isocyanate compound may include an isocyanate group (-NCO) and cause a urethane bond reaction with the hydroxy group-containing (meth) acrylate resin to serve as a curing agent.

Specifically, the isocyanate compound is, for example, 2,4- or 2,6-toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), 1 , 5-naphthalene diisocyanate, hexamethylene diisocyanate (HDI), propylene diisocyanate, lysine diisocyanate, 2,2,4- or 2,4,4-trimethylhexamerenedi isocyanate, 1,4-cyclohexanediisocyanate , Isophorone diisocyanate (IPDI), 4,4'-dicyclohexyl methane diisocyanate (H12MDI), and combinations thereof.

In one embodiment, the isocyanate compound may include hexamethylene diisocyanate (HDI), and the hexamethylene diisocyanate (HDI) is a biuret type HDI represented by Formula 1 below, It may include an isocyanurate type HDI, or both.

[Formula 1]

[Formula 2]

The matte decor sheet composition may include about 25 parts by weight to about 100 parts by weight of the isocyanate compound based on 100 parts by weight of the hydroxy group-containing (meth) acrylate resin. By using the hydroxy group-containing (meth) acrylate resin and the isocyanate compound in such a weight ratio, it is easy to adjust the equivalent ratio of the hydroxy group (-OH) and the isocyanate group (-NCO) in the above-mentioned range, The composition for matte decor sheet can secure a viscosity suitable for coating and curing.

The catalyst may include one or more selected from the group consisting of platinum, zinc, amine compounds and combinations thereof. The catalyst may serve to promote thermal curing of the composition for the matte decor sheet.

Another embodiment of the present invention sequentially provides a matte decor sheet comprising a primer layer, a hard coating layer, a matte release layer and a base layer. In this case, the hard coating layer and the matte release layer each include a thermoset of the composition for the matte decorative sheet according to the above. That is, the composition for the matte decor sheet includes a hydroxy group-containing (meth) acrylate resin, an isocyanate compound and a catalyst, the equivalent ratio of hydroxy group (-OH) to isocyanate group (-NCO) 1: 0.1 to 1: 1 to be. Matters relating to the composition for the matte decor sheet and each component thereof are as described above.

1 schematically shows the structure of the matte decorative sheet 100 according to an embodiment. Referring to FIG. 1, the matte decor sheet 100 may include a primer layer 110, a hard coating layer 120, a matte release layer 130, and a base layer 140.

The primer layer 110 is a layer having an adhesive property so that the matte decorative sheet 100 can be attached to the adherend to be decorated.

The primer layer 110 may include one selected from the group consisting of an acrylic adhesive, a silicone adhesive, an epoxy adhesive, a urethane adhesive, and a combination thereof.

The primer layer 110 may have a thickness of about 1 μm to about 3 μm. By maintaining the thickness of the primer layer 110 in the range through which the matte decorative sheet 100 can be firmly attached to the adherend, by appropriately securing the interface adhesion with the hard coating layer 120 to the matt Workability and formability of the curved surface of the decor sheet 100 may also be improved. When the thickness of the primer layer 110 exceeds the range, there may be a problem that the elongation of the matte decorative sheet 100 is lowered, if less than the range, the primer layer 110 is not uniformly coated You may have problems.

The base layer 140 may be used as a basic structure for forming the matte release layer 130, and after the matte decor sheet 100 is applied to the adherend, the base layer 140 is peeled off from the matte release layer 130. Layer to be removed.

Specifically, the base layer may include one or more selected from the group consisting of polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyethylene terephthalate glycol (PETG), and combinations thereof.

In one embodiment, the base layer may include polyethylene terephthalate (PET), in this case, improved in forming the matte release layer 130 by the method of thermosetting on one surface of the base layer 140 Heat resistance can be achieved. In addition, the flatness of the interface between the matte release layer 130 and the base layer 140 is secured to a certain level, when the matte sheet is finally applied to the adherend, the matte release layer 130 has a matt effect While showing the advantages can be obtained to implement a good appearance.

In one embodiment, the thickness of the base layer 140 may be about 30㎛ to about 50㎛. Since the thickness of the base layer 140 satisfies the above range, the matte release layer 130 may be formed on the upper portion of the base layer 140 so that the base layer 140 may be easily transferred onto the hard coating layer 140. Removal of the substrate layer 140 after applying to the complex may also be easy. If the thickness of the base layer 140 is too thin, wrinkles may occur in the base layer 140, which may cause a problem in that the matte release layer 130 is not easily formed on the base layer 140.

The matte release layer 130 and the hard coating layer 120 is located on the top of the matte decorative sheet 100 to be exposed to the outside, to realize the gloss of the surface to a matte, and to prevent contamination and scratches To perform.

Specifically, both the matte release layer 130 and the hard coating layer 120 is based on the thermosetting of the composition for the matte decorative sheet. As a result, compatibility and adhesion between the matte release layer 130 and the hard coat layer 120 may be improved, and the overall formability and durability of the matte decor sheet 100 may be improved.

The matte decorative sheet composition (hereinafter, referred to as 'hard coating layer forming composition') for forming the hard coating layer 120 is about 0.01 weight of the catalyst based on 100 parts by weight of the hydroxy group-containing (meth) acrylate-based resin Parts to about 0.1 parts by weight. When the catalyst is less than about 0.01 part by weight, the thermal curing rate may be too slow. When the catalyst is more than about 0.1 part by weight, the catalyst remains on the surface of the cured product after the catalyst is cured to interface with the matte release layer 130 The problem of deteriorating physical properties may occur.

In addition, the hard coating layer-forming composition does not contain a matting agent. When the composition for forming the hard coating layer includes a matting agent, surface properties of the primer layer 110 side of the hard coating layer 120 may be lowered, and the interlayer in the laminated structure of the matte decorative sheet 110 may be reduced. There exists a possibility that interface adhesive force may become weak or durability may fall. In addition, when both of the matte release layer 130 and the hard coating layer 120 includes a matting agent, it may cause a problem that the pattern or color of the back surface is not easily seen by reducing visibility.

The average thickness of the hard coating layer 120 may be about 5㎛ to about 20㎛. When the average thickness of the hard coating layer 120 satisfies the above range, when the matte release layer 130 is transferred thereon, the distribution of the uneven shape may be uniformly transferred, whereby the matte decorative sheet is sufficient. Matte effect can be achieved.

The matte release layer 130 also includes a thermoset of the composition for the matte decor sheet, the composition for the matte decor sheet for forming the matte release layer 130 (hereinafter, referred to as 'matte release layer forming composition' May further include a slip agent, a matting agent, or both.

The slip agent is a component that facilitates interfacial peeling between the matte release layer 130 and the base layer 140, and may include, for example, a copolymer of polydialkylsiloxane and polyoxyalkylene.

The polydialkylsiloxane may include, for example, a polydialkylsiloxane polymer capped at both ends of a hydroxyl group, and specifically, may be a polymer represented by the following Chemical Formula 3:

[Formula 3]

In Formula 3, R ¹ and R ² may each independently be an alkyl group having 1 to 3 carbon atoms, and each of them may be the same or different. In addition, R ³ and R ⁴ may each independently be an alkylene group having 1 to 3 carbon atoms, and each of them may be the same or different. In addition, n may be an integer of 1 to 12, for example, an integer of 1 to 6.

As the polydialkylsiloxane, by using a compound in which R ³ and R ⁴ are alkylene groups and n is within the above range, the desired physical properties of the matte release layer 130 can be easily implemented.

The polyoxyalkylene may be a polymer represented by the following formula (4).

[Formula 4]

In Formula 4, L may be a linear or branched alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 5.

When the composition for forming a matte release layer further includes a slip agent, the slip agent may include about 0.1 part by weight to about 2 parts by weight based on 100 parts by weight of the hydroxy group-containing (meth) acrylate resin. When the amount of the slip agent satisfies the range, when the matte decor sheet is applied to the final adherend, the base layer 140 and the matte release layer 130 can be easily peeled off, and at the same time, The release layer 130 may be firmly attached to the hard coating layer 120. When the content of the slip agent exceeds the above range, the surface energy is too low, it may be difficult to coat the composition for forming the matte release layer on the base layer 140.

In addition, the matting agent serves to implement the matte effect by imparting roughness to the surface of the matte release layer, for example, from the group consisting of silica particles, alumina particles, organic beads (bead) and combinations thereof It may include one or more selected.

In detail, the quencher may include silica particles, and the silica particles may include fumed silica. The pores of the silica particles may be about 0.2 ml / g or more, for example, about 0.4 ml / g to about 2.0 ml / g. That is, a volume of about 0.2 ml or more, for example, about 0.4 ml to about 2.0 ml, per 1 g of the silica particles may be voids. Since the matting agent contains silica particles having such physical properties, the matting agent rises to the surface of the matte release layer during the process of applying, drying and curing the matte release layer-forming composition, thereby increasing the probability of diffused reflection and improving matting. You can get the benefit of implementing the effect.

 An interface between the matte release layer 130 and the base layer 140 because the matting release layer-forming composition includes a matting agent; An interface between the matte release layer 130 and the hard coating layer 120; Or both of them can be formed in the concave-convex shape, thereby the matte decorative sheet 100 can implement an excellent matt effect.

For example, by using a matting agent particles having a particle size of micro (micro) unit can be given a concave-convex having an appropriate depth to implement a matte effect using the diffuse reflection effect by light, it is possible to implement the texture of the appropriate surface.

Specifically, the matting agent may have a particle diameter of about 1 μm to about 10 μm. The particle size of the matting agent refers to the average diameter of the particle cross-section, it can be measured by the number average particle diameter by TEM / SEM image analysis. The matte release layer includes a matting agent having a particle size in the above range, it is possible to implement an appropriate concave-convex shape compared to the thickness of the matte release layer, it can be implemented with a matte effect and also stain resistance.

The larger the size of the matting agent may be able to express a lower gloss even with a smaller content. However, the larger the size of the matting agent affects the surface touch. Excellent surface touch can be secured at the same time.

In one embodiment, the quencher may be used by mixing the first quencher having a particle size of about 1 ㎛ or less, less than about 5 ㎛ and a second quencher having a particle size of about 5 ㎛ or more, about 10 ㎛ or less.

When the composition for forming a matte release layer further includes the quencher, about 3 parts by weight to about 25 parts by weight of the quencher based on 100 parts by weight of the hydroxy group-containing (meth) acrylate resin, for example, about Greater than 5 parts by weight, about 20 parts by weight or less, for example, greater than about 5 parts by weight, and about 15 parts by weight or less. Since the matting agent is included in the weight part range, irregularities may be uniformly formed on one surface thereof, and the matting effect, stain resistance, and surface texture may be excellently realized.

The matte release layer-forming composition may further include a melamine compound. The melamine compound serves to improve the surface hardness of the matte release layer 130, and may include, for example, hexamethoxymethylmelamine, methylated melamine-formaldehyde, or the like.

When the composition for forming a matte release layer includes the melamine compound, the melamine compound may include about 80 parts by weight to about 100 parts by weight based on 100 parts by weight of the hydroxy group-containing (meth) acrylate resin. By including the melamine compound in the weight part range, it is possible to maximize the surface hardness improvement effect.

The matte release layer-forming composition may include about 0.5 parts by weight to about 5 parts by weight of the catalyst based on 100 parts by weight of the hydroxy group-containing (meth) acrylate resin. By including the catalyst in the weight part range, the curing time may be shortened.

The average thickness of the matte release layer may be about 5㎛ to about 20㎛, for example, may be about 7㎛ to about 12㎛. Since the average thickness of the matte release layer satisfies the above range, an excellent matting effect can be obtained even when a small amount of the matting agent is used. When the average thickness of the matte release layer is less than the range, there may be a problem that the distribution of the matting agent in the matte release layer is non-uniform, and when the matte release layer is exceeded, the matting agent does not transition during the manufacture of the matte decorative sheet is sufficient. There is a fear that the matte effect may not be realized.

In addition, by adjusting the average thickness of the matte release layer and the particle size and content of the matting agent to meet the above-mentioned range, the matte decorative sheet can achieve the desired gloss, stain resistance and surface hardness at the same time.

FIG. 3 schematically illustrates an enlarged view of a cross section of the matte release layer 130 according to one embodiment of the present invention including a matting agent (A).

Referring to FIG. 3, in one embodiment, the particle diameter d1 of the matting agent A and the average thickness d2 of the matte release layer may have a difference of ± 5 μm, for example, ± 1 μm. An interface between the matte release layer 130 and the base layer 140 by setting the particle diameter d 1 of the matting agent A and the average thickness of the matte release layer d 2 equally or similarly; An interface between the matte release layer 130 and the hard coating layer 120; Alternatively, both of them may form an uneven pattern, and through this, a matte effect of a desired level may be pictorialized. In addition, it is possible to ensure excellent contamination resistance and surface hardness.

The hard coating layer and the matte release layer may be formed by thermosetting each composition based on the composition for the matte decorative sheet.

Each composition based on the composition for the matte decor sheet may be thermally cured by heat treatment at about 100 ° C. to about 130 ° C. for about 1 minute to about 3 minutes. If the thermal curing is less than the temperature and time range may be a problem of less curing, if the temperature and time range is exceeded may cause a problem that heat-wrinkling occurs.

Method for manufacturing the matte decorative sheet 100 according to an embodiment of the present invention is not particularly limited, for example, may be as described below.

In one embodiment, the matte decorative sheet 100 is the coating and drying the composition for forming a matte release layer on the base layer 140, the composition for forming a hard coating layer on the composition for forming a matte release layer. The coating and drying may be prepared by coating and drying the adhesive for forming the primer layer on the composition for forming the hard coating layer.

In this case, the matte release layer-forming composition and the hard coating layer-forming composition may be dried by heat treatment for about 1 minute to about 3 minutes at about 100 ℃ to about 130 ℃, respectively. By drying at a temperature and time in the above range it can be cured to have an appropriate hardness and at the same time prevent damage to other components in the composition.

The composition for forming a matte release layer and the composition for forming a hard coating layer are subjected to an aging process for about 24 hours to about 48 hours at about 40 ° C. to about 60 ° C. after drying to the final matte release layer and hard coating layer. Can be prepared. Through this aging procedure, the interfacial adhesion between the matte release layer and the hard coating layer is excellent, and excellent scratch resistance can be secured by increasing the surface hardness.

Figure 2 schematically shows a method of applying the matte decorative sheet 100 according to an embodiment of the present invention. Referring to FIG. 2, the matte decor sheet 100 may be attached to the adherend 150, and then the base layer 140 may be peeled off from the matte release layer 120 to be finally applied.

The adherent 150 is an object to which the final decorative effect is given through the matte decor sheet 100, the material is not particularly limited, for example, polyvinyl chloride (PVC), glycol modified polyethylene terephthalate (PETG), amorphous polyethylene terephthalate (Amorphous PET, A-PET) may be made of a material. In addition, the shape of the adherend 150 is not particularly limited, and for example, may be a shape having a curved surface, or may be a planar shape. The matte decor sheet 100 may exhibit excellent adhesion to the adherend 150 formed of such a material and shape without generating wrinkles.

Specifically, the matte decorative sheet 100 may be attached to the adherent 150 by attaching its primer layer 110 to abut the adherend 150, and then heat-laminated.

In this case, the heat-lamination may be performed at a temperature of about 70 ℃ to about 90 ℃. When the temperature condition of the heat-lamination is less than the range, there may be a problem that the interface adhesion between the adherent 150 and the primer layer 110 is lowered, if the temperature exceeds the range, the subsequent It is difficult to easily peel off the base layer 140 from the matte release layer 120, and the main components of the matte release layer 130 and the hard coating layer 120 and the adherent 150 may be damaged. Can be.

After the matte decor sheet 100 is attached to the adherent 150 through heat-lamination, the base layer 140 may be released from the matte release layer 130 at a necessary time, thereby providing a desired decorative effect. have. When the base layer 140 is peeled from the matte release layer 130, some components of the matte release layer 130 may not be completely peeled from the base layer 140, but may be peeled off together. However, most of the matte release layer 130 is firmly attached to the hard coating layer 120 to form the outermost surface of the matte decorative sheet 100.

That is, in the adherent 150 to which the matte decor sheet 100 is applied, the matte release layer 130 is positioned on the outermost surface, and an interface between the hard coating layer 120 and the matte release layer 130. ; Alternatively, an excellent matt effect may be realized by an uneven pattern formed on the outermost surface of the matte release layer 130.

The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.

< Example  And Comparative example >

Example  One

A substrate layer having a thickness of 250 μm of polyethylene terephthalate (PET) was prepared. Subsequently, the equivalent ratio of hydroxy group-containing acrylate resin and biuret type hexamethylene diisocyanate (HDI) compound (Asahi-kasei Co., 24A-100) to hydroxy group (-OH) and isocyanate group (-NCO) is 1: 80 parts by weight of methoxylated melamine-formaldehyde as a melamine compound, 10 parts by weight of dibutyl tin dilaruate as a catalyst, and a slip agent based on 100 parts by weight of the hydroxy group-containing acrylate resin. 4 parts by weight of a copolymer of polydimethylsiloxane and polyoxyethylene capped with a hydroxyl group at both ends and 10 parts by weight of synthetic amorphous silicon dioxide having a particle diameter of 10 μm. By mixing, a composition for forming a matte release layer was prepared.

The hydroxy value (OH value) of the hydroxy group-containing acrylate resin was 30, the glass transition temperature was 98 ℃, the weight average molecular weight was 50,000.

Applying the composition for forming the matte release layer on one surface of the substrate layer, dried at 120 ° C for 1 minute, and then aged at 50 ° C for 24 hours to laminate a matte release layer having an average thickness of 10 ㎛ It was.

Thereafter, a composition for forming a hard coat layer having the same composition as the composition for forming a matte release layer was prepared, except that the melamine compound, the slip agent, and the matting agent were excluded.

After coating the composition for forming the hard coating layer on one surface of the matte release layer, and dried for 1 minute at 120 ℃, then aged at 50 ℃ for 24 hours to laminate a hard coating layer having an average thickness of 10 ㎛ It was.

Subsequently, a primer layer made of an acrylic adhesive was laminated on the hard coat layer to prepare a matte decor sheet.

Example  2

The matte decor sheet was manufactured under the same conditions and methods as in Example 1 except that the matting agent of the composition for forming a matte release layer was 5 μm.

Example  3

The matte decor sheet was manufactured under the same conditions and methods as in Example 1 except that the average thickness of the matte release layer was 15 μm.

Example  4

A matte decor sheet was manufactured under the same conditions and methods as in Example 1 except that 5 parts by weight of the matting agent of the composition for forming a matte release layer was used.

Comparative example  One

In each of the composition for forming a hard coat layer and the composition for forming a matte release layer, the hydroxy group-containing acrylate resin and the biuret type hexamethylene diisocyanate (HDI) compound (Asahi-kasei, 24A-100) Was manufactured in the same conditions and methods as in Example 1 except that the equivalent ratio of the hydroxyl group (-OH) to the isocyanate group (-NCO) was 1: 2.

Comparative example  2

In each of the composition for forming a hard coat layer and the composition for forming a matte release layer, the hydroxy group-containing acrylate resin and the biuret type hexamethylene diisocyanate (HDI) compound (Asahi-kasei, 24A-100) Was prepared in the same conditions and methods as in Example 1 except that the equivalent ratio of hydroxy group (-OH) to isocyanate group (-NCO) was 1: 0.05.

<Evaluation>

Each of the matte decorative sheets according to Examples 1-4 and Comparative Examples 1-2 was attached such that its primer layer was in contact with a plastic adherend made of polyvinyl chloride (PVC). Next, in Example 1-4 and Comparative Example 1-2, the base layer was peeled from the matte release layer.

Thereafter, various physical properties of each of the matte decorative sheets were evaluated as described in Table 1 below.

Experimental Example  1: Measurement of Surface Strength

For each matte decor sheet according to Example 1-4 and Comparative Example 1-2, the pencil hardness of the surface of the hard coating layer was measured using an electric pencil hardness tester (coretech). The pencil hardness increases in the order of 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H and 9H, and the surface increases as the pencil hardness increases. It can be seen that the strength is excellent. The results are as described in Table 1 below.

Experimental Example  2: Glossiness  Measure

For each matte decorative sheet according to Examples 1-4 and Comparative Examples 1-2, glossiness at 60 ° angle of the surface of the hard coating layer was measured using a gloss meter (BYK, gloss meter). Measured. The smaller the numerical value indicating glossiness, the better the matt effect. The results are as described in Table 1 below.

Experimental Example  3: Pollution-resistant  Measure

For each matte decorative sheet according to the Examples and Comparative Examples, the stain resistance of the surface of the hard coating layer was measured according to the standard standard 'DIN EN 12720: 1997-10, 1B or more', specifically, name pen, ink 3 drops of contaminants such as coffee, juice, wine, etc. on each matte decor sheet, and left for 16 hours at room temperature, followed by wiping the contaminants with a cloth moistened with water or alcohol, and whether the contaminants remain with the naked eye. Was observed.

 The grades were measured according to the evaluation criteria described below and listed in Table 1 below.

The evaluation criteria are based on the following 1) to 6).

1) Grade 1: Hard coating layer is damaged and there is a severe change in gloss or color, 2) Grade 2: Hard coating layer has a severe change that can be observed with naked eyes or color without change,

3) Grade 3: Light change of gloss or color without change of hard coating layer,

4) Grade 4: Minimal change in gloss or color,

5) Grade 5-No visible change,

6) Unrated: The hard coat layer is peeled off or destroyed.

Pencil hardness Glossiness Pollution degree Example 1 F 1.2 Grade 4 Example 2 F 1.6 Grade 4 Example 3 HB 2.1 Grade 4 Example 4 HB 1.4 Grade 4 Comparative Example 1 B 1.7 Grade 3 Comparative Example 2 F 1.6 Grade 2

Referring to the results of Table 1, the matte decor sheet of Example 1-4 according to an embodiment of the present invention is higher than the matte decor sheet of Comparative Example 1 wherein the equivalent ratio of hydroxy group to isocyanate group is 1: 2 It can be confirmed that the surface hardness and excellent stain resistance are shown.

In addition, it can be seen that the matte decor sheet of Example 1-4 exhibits excellent stain resistance compared to the matte decor sheet of Comparative Example 2 having an equivalent ratio of hydroxy group to isocyanate group of 1: 0.05.

In addition, in the matte decorative sheet of Example 1-4, Example 1 is the average thickness of the matte release layer and the particle size of the matting agent, the average thickness of the matte layer and the particle size of the matting agent Compared to Examples 2 and 3 with a difference of 5 μm, it can be seen that the surface hardness and contamination resistance are realized together with the matt effect due to the glossiness of about 1.0 to about 1.5.

100: matte decor sheet
110: primer layer
120: hard coating layer
130: matt release layer
140: substrate layer
150: adherend

Claims (15)

Sequentially comprising a primer layer, a hard coating layer, a matte release layer and a base layer,
The hard coating layer and the matte release layer each include a thermoset of the composition for matte decorative sheet,
The composition for matte decor sheet comprises a hydroxyl group-containing (meth) acrylate resin, an isocyanate compound and a catalyst, the equivalent ratio of hydroxy group (-OH) to isocyanate group (-NCO) is 1: 0.1 to 1: 1,
The matte release layer includes a matting agent,
The hard coating layer does not contain a matting agent,
The quencher has a particle diameter of 1㎛ 10㎛,
100 parts by weight of the hydroxy group-containing (meth) acrylate-based resin, including more than 5 parts by weight, 20 parts by weight or less,
The average thickness of the matte release layer is 5㎛ to 20㎛,
The average thickness of the hard coating layer is 5㎛ to 20㎛
Matte decor sheet.
The method of claim 1,
The hydroxy group-containing (meth) acrylate resin is a copolymer of a monomer component containing an alkyl group-containing (meth) acrylate monomer and a hydroxy group-containing (meth) acrylate monomer.
Matte decor sheet.
The method of claim 1,
The hydroxy group-containing (meth) acrylate resin has a weight average molecular weight (Mw) of 40,000 to 60,000
Matte decor sheet.
The method of claim 1,
The hydroxy group-containing (meth) acrylate-based resin has a glass transition temperature (Tg) of 40 ℃ to 120 ℃
Matte decor sheet.
The method of claim 1,
The hydroxy group-containing (meth) acrylate-based resin has a hydroxy value (OH value) of 20 to 100
Matte decor sheet.
The method of claim 1,
The isocyanate compound is 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), 1, 5-naphthalene diisocyanate, hexamethylene diisocyanate (HDI), propylene diisocyanate, lysine diisocyanate, 2,2,4- or 2,4,4-trimethylhexamerenedi isocyanate, 1,4-cyclohexanediisocyanate, At least one selected from the group consisting of isophorone diisocyanate (IPDI), 4,4'-dicyclohexyl methane diisocyanate (H12MDI), and combinations thereof
Matte decor sheet.
The method of claim 1,
The catalyst comprises at least one selected from the group consisting of platinum, zinc, amine compounds and combinations thereof.
Matte decor sheet.
delete The method of claim 1,
The matte release layer further comprises a slip agent
Matte decor sheet.
The method of claim 1,
The matting agent includes at least one selected from the group consisting of silica particles, alumina particles, organic beads, and combinations thereof.
Matte decor sheet.
delete The method of claim 9,
The slip agent comprises a copolymer of polydialkylsiloxane and polyoxyalkylene
Matte decor sheet.
delete The method of claim 1,
An interface between the matte release layer and the base layer; An interface between the matte release layer and the hard coating layer; Or all of them contain irregularities
Matte decor sheet.
The method of claim 1,
The adherend is attached to the primer layer,
Used as a method in which the base layer is peeled from the matte release layer
Matte decor sheet.

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